Fuel additive composition

ABSTRACT

A fuel additive composition including a Mannich product, a polyetheramine, and a friction modifier is disclosed. Also, disclosed are a fuel composition comprising the fuel additive composition, an engine combusting the fuel composition, and a method of preventing and/or forming deposits in an engine.

FIELD

The present invention relates to a fuel additive composition comprisinga detergent, such as a Mannich product, a dispersant, such as apolyetheramine, and a friction modifier, such as an amide. The fueladditive composition may be useful in compositions such as, e.g., fuelcompositions.

Introduction

Fuels used in internal combustion engines generally contain componentsthat lead to the formation of undesirable engine deposits. It isbelieved that these deposits can negatively affect engine performanceby, for example, clogging fuel induction systems. Considerable researchhas been devoted to additives for controlling (preventing or reducing)deposit formation in internal combustion engines. The preparation andidentification of fuel additives capable of controlling undesirabledeposit formation has been a focal point of this research.

In recent years, several automobile manufacturers jointly created new,voluntary deposit control standards for gasoline. The purpose was todefine a new class of commercial gasoline with enhanced detergencycalled TOP TIER detergent gasoline. A document entitled, “TOP TIERDetergent Gasoline Deposit Control Performance Standards,” wasintroduced at the American Petroleum Institute's 33^(rd) Automotive,Petroleum Industry Forum on Apr. 6, 2004, the disclosure of which ishereby incorporated by reference. These standards include the followingtest methods: intake valve keep clean initial performance, combustionchamber deposit initial performance, fuel injector fouling initialperformance, determination of deposit control additive performance, andintake valve sticking initial performance.

Thus, there exists a need in the industry for fuels and fuel additivepackages that will meet the TOP TIER performance standards.

SUMMARY

According to various aspects of the disclosure, there is provided a fueladditive composition comprising a Mannich product, a polyetheramine, anda friction modifier; and a process for preparing a fuel additive,comprising providing a Mannich product, a polyetheramine, and a frictionmodifier to yield a fuel additive.

It is to be understood that both the foregoing general description andthe following description of various embodiments are exemplary andexplanatory only and are not restrictive.

DESCRIPTION OF VARIOUS EMBODIMENTS

The disclosed fuel additive composition may, in one embodiment, comprisea detergent, such as a Mannich product. The Mannich product may be afuel-soluble reaction product obtained by the reaction of i) an amine;ii) an alkyl-substituted hydroxyaromatic compound; and iii) an aldehyde.In an embodiment, the Mannich product may be a reaction product obtainedby the reaction of a low molecular weight alkyl-substitutedhydroxyaromatic compound, an aldehyde, and an amino-alcohol as disclosedin U.S. Pat. No. 6,176,886, the disclosure of which is incorporated byreference.

Amines suitable for use as component i) may comprise at least oneprimary or secondary amine group and may further comprise at least onehydroxyl group. In other embodiments, the amine reactants may beamino-alcohols; alkoxylated amines; and mixtures thereof. Non-limitingexamples of suitable amino-alcohols include ethanolamine anddiethanolamine. Non-limiting examples of alkoxylated amines includeethoxylated and propoxylated amines and polyamines. An example of theseamines includes, for example, 2-(2-aminoethylamino) ethanol. In anotherembodiment, diethanolamine may be used.

Polyamines suitable for use as the amine in the formation of the Mannichmay comprise at least two amine groups wherein at least one of the aminegroups is a primary or secondary amine. Non-limiting examples ofpolyamines include alkylene polyamines comprising at least one suitablyreactive primary or secondary amino group in the molecule. Othersubstituents may be present in the polyamine. In an embodiment, thealkylene polyamine may be a polyethylene polyamine. Suitable alkylenepolyamine reactants include ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,hexaethyleneheptamine, heptaethylene octamine, octaethylenenonamine,nonaethylenedecamine, decaethyleneundecamine and mixtures of such amineshaving nitrogen contents corresponding to alkylene polyamines of theformula H₂N-(A-NH—)_(n)H, wherein A may be a divalent ethylene orpropylene and n may be an integer of from about 1 to about 10. Thealkylene polyamines may be obtained by the reaction of ammonia anddihalo alkanes, such as dichloro alkanes. Thus, the alkylene polyaminesobtained from the reaction of about 2 to about 11 moles of ammonia withabout 1 to about 10 moles of dichloro alkanes comprising about 2 toabout 6 carbon atoms and the chlorines on different carbon atoms may besuitable alkylene polyamine reactants.

In another embodiment, the amine may be a polyamine comprising at leastone primary or secondary amino group and at least one tertiary aminogroup in the molecule. Examples of suitable polyamines includeN,N,N″,N″-tetraalkyldialkylenetriamines (two terminal tertiary aminogroups and one central secondary amino group),N,N,N′,N″-tetraalkyltrialkylenetetramines (one terminal tertiary aminogroup, two internal tertiary amino groups and one terminal primary aminogroup), N,N,N′,N″,N′″-pentaalkyltrialkylenetetramines (one terminaltertiary amino group, two internal tertiary amino groups and oneterminal secondary amino group),tris(dialkylaminoalkyl)aminoalkylmethanes (three terminal tertiary aminogroups and one terminal primary amino group), and like compounds,wherein the alkyl groups may be the same or different and may compriseno more than about 12 carbon atoms each, and which, for example, maycomprise from about 1 to about 4 carbon atoms each. For example, thesealkyl groups may be methyl and/or ethyl groups. In certain embodiments,the polyamine reactants include N,N-dimethyl-1,3-propanediamine andN-methyl piperazine.

The ii) alkyl-substituted hydroxyaromatic compounds and iii) aldehydesused in making the Mannich product may be any such compounds known andapplied in the art, in accordance with the foregoing limitations.

Representative ii) alkyl-substituted hydroxyaromatic compounds that maybe used in forming the Mannich product may include, but are not limitedto, polypropylphenol (formed by alkylating phenol with polypropylene),polybutylphenols (formed by alkylating phenol with polybutenes and/orpolyisobutylene), and polybutyl-co-polypropylphenols (formed byalkylating phenol with a copolymer of butylene and/or butylene andpropylene). In an embodiment, the alkyl-substituted hydroxyaromaticcompound may be chosen from polyolefin-substituted phenols, such aspolybutylene-substituted phenols, polypropylene-substituted phenols, andfor example polyisobutycresols.

Other similar long-chain alkylphenols may also be used. Non-limitingexamples include phenols alkylated with copolymers of butylene and/orisobutylene and/or propylene, and at least one mono-olefinic comonomerscopolymerizable therewith (e.g., ethylene, 1-pentene, 1-hexene,1-octene, 1-decene, etc.) where the copolymer molecule comprises atleast 50% by weight, of butylene and/or isobutylene and/or propyleneunits. The comonomers polymerized with propylene or such butenes may bealiphatic and can also comprise non-aliphatic groups, e.g., styrene,o-methylstyrene, p-methylstyrene, divinyl benzene and the like. Thus, inany case, the resulting polymers and copolymers used in forming thealkyl-substituted hydroxyaromatic compounds may be substantiallyaliphatic hydrocarbon polymers. In an embodiment, the alkylphenol may bechosen from cresols.

Polybutylphenol (formed by alkylating phenol with polybutylene) may beused. Unless otherwise specified herein, the term “polybutylene” is usedin a generic sense to include polymers made from any and all “pure” or“substantially pure” 1-butene or isobutene, and polymers made frommixtures of two or all three of 1-butene, 2-butene and isobutene.Commercial grades of such polymers may also comprise insignificantamounts of other olefins. So-called high reactivity polybutylenes havingrelatively high proportions of polymer molecules having a terminalvinylidene group, formed by methods such as described, for example, inU.S. Pat. No. 4,152,499 and W. German Offenlegungsschrift 29 04 314, thedisclosures of both of which are hereby incorporated by reference, mayalso be suitable for use in forming the long chain alkylated phenolreactant.

The alkylation of the hydroxyaromatic compound may be performed in thepresence of an alkylating catalyst at a temperature in the range ofabout 50 to about 200° C. Acidic catalysts may be generally used topromote Friedel-Crafts alkylation. Catalysts used in commercialproduction include, for example, sulphuric acid, BF₃, aluminumphenoxide, methanesulphonic acid, cationic exchange resin, acidic claysand modified zeolites or other Lewis acids, such as tin halides.

The long chain alkyl substituents on the benzene ring of the phenoliccompound may be derived from polyolefin having a number averagemolecular weight (M_(n)) of from about 500 to about 3000 (for examplefrom about 500 to about 2100) as determined by gel permeationchromatography (GPC). In some embodiments, the polyolefin may have apolydispersity (weight average molecular weight/number average molecularweight) in the range of about 1 to about 4 (for example from about 1 toabout 2) as determined by GPC.

The Mannich product may be, for example, made from a long chainalkylphenol. However, other phenolic compounds may be used includinghigh molecular weight alkyl-substituted derivatives of resorcinol,hydroquinone, catechol, hydroxydiphenyl, benzylphenol, phenethylphenol,naphthol, tolyinaphthol, among others. In embodiments, the Mannichproduct may be prepared from polyalkylphenol reactants, e.g.,polypropylphenol and polybutylphenol whose alkyl group has a numberaverage molecular weight of about 500 to about 2100, wherein the alkylgroup may be a polybutyl group derived from polybutylene having a numberaverage molecular weight in the range of about 800 to about 1300.

A configuration of the alkyl-substituted hydroxyaromatic compound may bethat of a para-substituted mono-alkylphenol. However, any alkylphenolreadily reactive in the Mannich condensation reaction may be employed.The long chain alkyl substituents may contain some residualunsaturation, but in general, may be substantially saturated branched orlinear alkyl groups.

Representative iii) aldehydes for use in the preparation of the Mannichproduct include, but are not limited to, aliphatic aldehydes such asformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,valeraldehyde, caproaldehyde, heptaldehyde, stearaldehyde. Aromaticaldehydes which may be used include benzaldehyde and salicylaldehyde.Illustrative heterocyclic aldehydes for use herein are furfural andthiophene aldehyde, etc. Also useful may be formaldehyde-producingreagents such as paraformaldehyde, or aqueous formaldehyde solutionssuch as formalin. In an embodiment, formaldehyde or formalin may beused.

Components i), ii), and iii) may be reacted under suitable Mannichreaction conditions to form a Mannich product. The condensation reactionamong the alkyl-substituted hydroxyaromatic compound, the amine, and thealdehyde may be conducted at a temperature in the range of about 40° toabout 200° C. The reaction can be conducted in bulk (no diluent orsolvent) or in a solvent or diluent. Water may be evolved and can beremoved by azeotropic distillation during the course of the reaction.The Mannich product may be formed, in one embodiment, by reacting thealkyl-substituted hydroxyaromatic compound, the amine, and the aldehydein the molar ratio of 1.0:0.2-1.8:1.0-4.0, respectively, for example1:0.5-1.5:1.5-2.5. The aldehyde may be present in a molar amount atleast equal to the total molar amount of the amine compound present.

The detergent may be present in the fuel additive composition in anyamount sufficient to reduce and/or prevent the formation of deposits,such as intake valve and chamber combustion valves. In an embodiment,the Mannich product may comprise from about 5 ptb to about 300 ptb, forexample from about 25 ptb to about 200 ptb, and as a further examplefrom about 75 to about 150 ptb, of active material in the fuelcomposition. Commercial examples of a Mannich product include HiTEC®6416 (Ethyl Corp., Richmond, Va.).

The disclosed fuel additive composition may comprise reaction productsof the Mannich product. For example, the fuel additive composition may,in one embodiment, comprise up to 15% by weight of unreactedpolyisobutylene phenol, and/or up to 10% by weight of unreactedpolyisobutylene.

The fuel additive composition may also comprise a dispersant, such as apolyetheramine or polyether. The disclosed polyetheramine may berepresented by the formula R(OCH₂CH(R¹))_(n)A wherein R may be ahydrocarbyl group comprising from C₁-C₃₀, R¹ may be selected from thegroup consisting of hydrogen, hydrocarbyl groups comprising from about 1to about 16 carbon atoms, and mixtures thereof; n may be a number fromabout 2 to about 50; and A may be selected from the group consisting of—OCH₂CH₂CH₂NR²R² and —NR³R³ wherein each R² may be independentlyhydrogen or hydrocarbyl comprising from about C₁-C₁₆, and each R³ may beindependently hydrogen, hydrocarbyl or —(R⁴N(R⁵))_(p)R⁶ wherein R⁴ maybe C₂-C₁₀ alkylene, and R⁵ and R⁶ may be independently hydrogen orhydrocarbyl, and p may be a number from about 1 to about 7.

These polyetheramines can be prepared by initially condensing an alcoholor alkylphenol with an alkylene oxide, mixture of alkylene oxides orwith several alkylene oxides in sequential fashion in, for example, a1:2-50 mole ratio of hydric compound to alkylene oxide to form apolyether intermediate. U.S. Pat. No. 5,094,667 provides reactionconditions for preparing a polyether intermediate, the disclosure ofwhich is incorporated herein by reference. U.S. Pat. No. 5,952,261provides double metal cyanide complex catalysts which can be used topolymerize epoxides to provide polyether polyols having low levels ofunsaturation and/or high molecular weights, the disclosure of which ishereby incorporated by reference.

The alcohols can be linear or branched from about 1 to about 30 carbonatoms, for example from about 6 to about 20 carbon atoms, and as afurther example from about 10 to about 16 carbon atoms. The alkyl groupof the alkylphenols can comprise from about 1 to about 30 carbon atoms,and for example from about 10 to about 20 carbon atoms.

The alkylene oxides may be selected from the group consisting ofethylene oxide, propylene oxide, and butylene oxide. The number ofalkylene oxide units in the polyether intermediate may be from about 10to about 35, and for example from about 18 to about 27.

The polyether intermediate can be converted to a polyetheramine byamination with ammonia, an amine or a polyamine to form a polyetheramineof the type where A may be —NR³R³, wherein R³ may be as defined above.Published Patent Application EP310875 provides reaction conditions forthe amination reaction, the disclosure of which is incorporated hereinby reference. Alternately, the polyether intermediate can also beconverted to a polyetheramine of the type where A may be—OCH₂CH₂CH₂NR²R², wherein R³ may be as defined above, by reaction withacrylonitrile followed by hydrogenation. U.S. Pat. No. 5,094,667provides reaction conditions for the cyanoethylation and subsequenthydrogenation, the disclosure of which is incorporated herein byreference.

In some embodiments, the polyetheramines wherein A may be —OCH₂CH₂CH₂NH₂may be used. Commercial examples of suitable polyetheramines are theTECHRON® series from Chevron, the JEFFAMINE® series from Huntsman, andthe HiTEC® from Afton Chemical Corp.

The disclosed polyethers may be represented by the formulaR⁷O(CH₂CH(R⁸)O)_(q)H wherein R⁷ may be a hydrocarbyl group comprisingfrom about 1 to about 30 carbon atoms, R⁸ may be selected from the groupconsisting of hydrogen, hydrocarbyl groups comprising from about 1 toabout 16 carbon atoms, and mixtures thereof, and q may be a number fromabout 2 to about 50. Reaction conditions for preparation as well as someembodiments of the disclosed polyethers were presented above in thepolyetheramine description for the polyether intermediate. A commercialexample of a polyether is the Bayer ACTACLEAR® series. Suitable samplesmay also be available from Dow Chemicals, Huntsman, BASF, and ICI.

The dispersant, such as the polyetheramine, may comprise from about 5ptb to about 300 ptb, for example from about 25 ptb to about 200 ptb,and as a further example from about 75 to about 150 ptb, of activematerial in the fuel composition. The dispersant may be present in thefuel additive composition in an amount of from about 5 to about 60% byweight of active material relative to the total weight of thecomposition. The disclosed fuel additive composition may comprisereaction products of the polyetheramine. The fuel additive compositionmay further comprise up to 25% by weight of unreacted starting material,such as polyether alcohol.

In an embodiment, the polyetheramine disclosed herein may not be afriction modifier.

The disclosed fuel additive composition will also comprise a frictionmodifier. The friction modifier may be an amide obtained from a reactionof an amine with an acid. Both the amine and the acid may independentlybe monofunctional or multifunctional. For example, a monoamine may bereacted with a dimer acid to form an amide suitable for use herein.Alternatively, a polyamine may be reacted with a monoacid to form anamide. One of ordinary skill in the art would readily know all thevarious types of acids and amines that could be reacted in variouspermutations and combinations in order to achieve an amide.

In an embodiment, the friction modifier may be an amide, such as areaction product of a monocarboxylic fatty acid with an amine, such asdiethanolamine and its derivatives, to form a monocarboxylic fatty acidamide. Diethanolamine derivatives suitable for use as the amine hereinto produce the amide friction modifier include, but are not limited to,fatty acid amides and esters of diethanolamine, and mixtures thereof.The fatty acid amides or esters of diethanolamine can be made by forminga mixture of a fatty acid and diethanolamine and heating the mixture toremove water. Optionally, a water immiscible inert solvent such astoluene or xylene can be included to aid in the removal of water.Optionally, a fatty ester may be substituted for the fatty aciddescribed above and reacted directly with the amine.

In preparing mixtures, according to one embodiment of the presentinvention, about 1 to about 3 moles of fatty acid may be used per moleof amine, such as diethanolamine. The reaction proceeds to yield mainlyamide according to the following equation:

wherein R may be a hydrocarbon residue of the fatty acid.

Some of the diethanolamine can react to form an ester according to thefollowing equation:

The above reaction products can be separated by distillation and usedseparately in diesel or gasoline fuel compositions. For example, theymay not be separated, but may be used as mixtures. The mixtures can alsocontain fatty acid ester-amides of diethanolamine. When equal molemixtures of fatty acid and diethanolamine are reacted, very littleester-amide forms. However, whenever more than one mole of fatty acid isreacted with a mole of diethanolamine, increased amounts of ester-amidecan form according to the following equations:

Such ester-amides are within the scope of the present disclosure.

In some embodiments, the fatty acids used in making the diethanolaminederivatives useful in the present disclosure may be those comprisingfrom about 8 to about 20 carbon atoms. Non-limiting examples of theseinclude caprylic acid, pelargonic acid, capric acid, isostearic acid,undecylic acid, lauric acid, tridecoic acid, myristic acid, stearicacid, arachidic acid, and mixtures thereof.

For example, the fatty acid may be an unsaturated fatty acid such ashypogeic acid, oleic acid, elaidic acid, erucic acid, brassidic acid,and the like. As a further example, the fatty acid may be oleic acid.Thus, suitable additives are N,N-bis-(2-hydroxyethyl)oleamide,N-(2-hydroxyethyl)aminoethyl oleate, and mixtures thereof. Thediethanolamine derivatives suitable for use herein include those taughtin U.S. Pat. No. 4,204,481, the disclosure of which is herebyincorporated by reference.

The friction modifier may be present in the fuel additive composition ina friction modifying amount. Commercial examples of a friction modifier,for use in the disclosed fuel additive, include, but are not limited toHiTEC® 4848A, and HiTEC® 6457 from Afton Chemical Corp., Richmond, Va.Friction modifying amount as determined by ASTM D 6079, which is astandard method for determining lubricity in a “high-frequencyreciprocating rig” (HFRR). In various embodiments, olea amides may beused. For example, ethomids, such as N-(hydroxyethyl)penta-(oxyalkylene)oleamide; and schercomids, such as ethoxylated fatty amides, for exampleschercomid SOA-E (ethoxylated fatty C₁₈ amide) and SCHERCOMID SL-ML, maybe used.

The disclosed fuel additive composition may also optionally comprise afluidizer, such as a polyether alcohol, for example polyethermonool. Thepolyether alcohol may be present in the fuel additive composition as anunreacted byproduct of the polyetheramide reaction.

The fuel additive composition of the present disclosure may optionallycontain at least one supplemental additive. The at least onesupplemental additive may be chosen from, for example, dispersants,detergents, antioxidants, carrier fluids, metal deactivators, dyes,markers, corrosion inhibitors, biocides, antistatic additives,drag-reducing agents, demulsifiers, dehazers, anti-icing additives,anti-knock additives, anti-valve-seat recession additives, lubricityadditives, multifunctional additives (e.g., methylcyclopentadienylmanganese tricarbonyl, MMT®, Afton Chemical Corp., Richmond, Va., and/orother cyclopentadienyl manganese tricarbonyl compounds), and combustionimprovers. The at least one supplemental additive may be provided in thefuel composition in an amount necessary to achieve the desired effect.

The base fuels used in formulating the fuel compositions according tothe present disclosure include any base fuels suitable for use in theoperation of spark-ignition internal combustion engines, such as leadedor unleaded motor and aviation gasolines, diesel, and so-calledreformulated gasolines which typically contain both hydrocarbons of thegasoline boiling range and fuel-soluble oxygenated blending agents, suchas alcohols, ethers and other suitable oxygen-containing organiccompounds. Suitable oxygenates include, for example, methanol, ethanol,isopropanol, t-butanol, mixed C₁ to C₅ alcohols, methyl tertiary butylether, tertiary amyl methyl ether, ethyl tertiary butyl ether, and mixedethers. Oxygenates, when used, will normally be present in the base fuelin an amount below about 25% by volume, for example in an amount thatprovides an oxygen content in the overall fuel in the range of about 0.5to about 5% by volume.

Fuel compositions may comprise a major amount of a base fuel and a minoramount of a fuel additive composition. A “major amount” may beunderstood to mean greater than or equal to about 50%. A “minor amount”may be understood to mean less than about 50%.

According to one aspect of the present disclosure, the Mannich productmay be used in combination with at least one liquid carrier or inductionaid. Such carriers can be of various types such as, for example, liquidpoly-α-olefin oligomers, mineral oils, liquid poly(oxyalkylene)compounds, liquid alcohols or polyols, polyalkenes, liquid esters, andsimilar liquid carriers. Mixtures of two or more such carriers can beemployed.

The additives used in formulating the fuels disclosed herein can beblended into the base fuel individually or in various sub-combinations.However, it may be desirable in some instances to blend all of thecomponents concurrently using an additive concentrate (i.e., additivesplus a diluent, such as a hydrocarbon solvent). The use of an additiveconcentrate takes advantage of the mutual compatibility afforded by thecombination of ingredients when in the form of an additive concentrate.Also, use of a concentrate may reduce blending time and may lessen thepossibility of blending errors.

The fuel additive composition disclosed herein can contact an actuatedinjector. Non-limiting examples of an actuated injector includedirect-injection gasoline, port-fuel, sequential central port-fuel, anddirector plate injectors.

In another embodiment, a fuel additive composition may comprise analiphatic hydrocarbyl-substituted amine, a polyetheramine as disclosedherein, and a friction modifier as disclosed herein. In various aspectsof this embodiment, the polyetheramine may not be a friction modifier.

The aliphatic hydrocarbyl-substituted amine may be a straight orbranched chain hydrocarbyl-substituted amine comprising at least onebasic nitrogen atom wherein the hydrocarbyl group has a number averagemolecular weight of about 700 to about 3,000, for example from about 750to about 2,200, and as a further example from about 900 to about 1,500.In embodiments, the aliphatic amines may be of sufficient molecularweight so as to be nonvolatile at normal engine intake valve operatingtemperatures, such as in the range of about 175° C. to 300° C.

When employing a branched-chain hydrocarbyl amine, the hydrocarbyl groupmay be derived from polymers of C₂-C₆ olefins. In embodiments, thebranched-chain hydrocarbyl groups may be derived from polypropylene andpolyisobutylene and the branches may comprise from about 1 to about 2carbon atoms, for example 1 carbon atom, such as a methyl. Thebranched-chain hydrocarbyl amines may not be a pure single product, butrather a mixture of compounds having an average molecular weight.

The amine component of the aliphatic hydrocarbyl-substituted amine maybe derived from ammonia, a monoamine or a polyamine. The monoamine orpolyamine component may include a broad class of amines having fromabout 1 to about 12 amine nitrogen atoms and from about 1 to about 40carbon atoms with a carbon to nitrogen ratio ranging from about 1:1 to10:1. In most instances, the amine component may not be a pure singleproduct, but rather a mixture of compounds having a major quantity ofthe designated amine. For the more complicated polyamines, thecompositions will be a mixture of amines having as the major product thecompound indicated and having minor amounts of analogous compounds.Suitable monoamines and polyamines are described more fully below.

When the amine component is a polyamine, it may be a polyalkylenepolyamine, including alkylenediamine, wherein the alkylene group maycomprise from about 2 to about 6 carbon atoms. Non-limiting examples ofpolyamines include ethylene diamine, diethylene triamine, triethylenetetramine, tetraethylene pentamine, di(trimethylene) triamine, propylenediamine, dipropylene triamine, tripropylene tetraamine, andpentaethylene hexamine.

In an embodiment, the branched-chain hydrocarbyl amines may include, butare not limited to, polyisobutenyl ethylene diamine and polyisobutylamine, wherein the polyisobutyl group may be substantially saturated andthe amine moiety may be derived from ammonia.

Hydrocarbyl, as used in describing the amine moiety on the aliphaticamine employed in this invention, may denote an organic radicalcomprising carbon and hydrogen which may be aliphatic, alicyclic,aromatic or combinations thereof, e.g., aralkyl. In embodiments, thehydrocarbyl group may be relatively free of aliphatic unsaturation,i.e., ethylenic and acetylenic, for example acetylenic unsaturation.Non-limiting examples of hydrocarbyl groups and substituted hydrocarbylgroups include alkyls such as methyl, ethyl, propyl, butyl, isobutyl,pentyl, hexyl, octyl, etc., alkenyls such as propenyl, isobutenyl,hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl,3-hydroxypropyl, hydroxy-isopropyl, 4-hydroxybutyl, etc., ketoalkyls,such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy and lower alkenoxyalkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl,diethyleneoxymethyl, triethyleneoxyethyl, tetraethyleneoxyethyl,diethyleneoxyhexyl, etc.

The amine component also may be derived from heterocyclic polyamines,heterocyclic substituted amines and substituted heterocyclic compounds,wherein the heterocycle comprises at least one 5-6 membered ringscontaining oxygen and/or nitrogen. Such heterocyclic rings may besaturated or unsaturated and substituted. The heterocyclic compounds maybe exemplified by piperazines, such as 2-methylpiperazine,N-(2-hydroxyethyl)-piperazine, 1,2-bis-(N-piperazinyl)ethane andN,N′-bis(N-piperazinyl)piperazine, 2-methylimidazoline,3-aminopiperidine, 3-aminopyridine, and N-(3-aminopropyl)-morpholine,etc.

The aliphatic hydrocarbyl amines employed may be prepared byconventional procedures known in the art. See U.S. Pat. Nos. 5,993,499;3,438,757; 3,565,804; 3,574,576; 3,848,056; 3,960,515; and 4,832,702,the disclosures of which are incorporated herein by reference.

Other aspects of the present invention include methods for reducing theformation or persistence of deposits, such as intake valve deposits andchamber combustion deposits, in an engine and eliminating valve stickingin a spark-ignition engine by fueling and/or operating the engine withthe fuel composition disclosed herein.

EXAMPLE

A fuel additive composition comprising 23% by weight of polyetheramine,23% by weight of a Mannich product from high reactivity polyisobutylenecresol (HiTEC® 6416, Ethyl Corp., Richmond, Va.), 12% by weight of apolyether alcohol (ACTACLEAR 2400®, Bayer Corporation, Pittsburgh, Pa.),and 42% by weight of a solvent (A100, Exxon, Paulsboro, N.J.) wasblended into a fuel and tested on a SwRI PFI Rig according to ASTMD6421.

ASTM D6421 is a test method covering a bench test procedure to evaluatethe tendency of automotive spark-ignition engine fuel to foul electronicport fuel injectors (PFI). The test method utilizes a bench apparatusequipped with Bosch injectors specified for use in a 1985-1987 Chrysler2.2-L turbocharged engine. This test method is based on a test proceduredeveloped by the Coordinating Research Council (CRC) for prediction ofthe tendency of spark-ignition engine fuel to form deposits in the smallmetering clearances of injectors in a port fuel injection engine (seeCRC Report No. 5922). The test method is applicable to spark-ignitionengine fuels, which may contain antioxidants, corrosion inhibitors,metal deactivators, dyes, deposit control additives, demulsifiers, oroxygenates, or a combination thereof.

The data is as follows:

Run 1: 80 ptb (0.864 grams/gallon) of the above-identified fuel additivewas added to a gasoline. Injector 1 2 3 4 43.9 29.2 15.7 10.7 = 24.9%average

Run 2: 80 ptb (0.864 grams/gallon) of the above-identified fuel additiveand 20 ptb (0.216 grams/gallon) of a friction modifier (HiTEC® 6457,Afton Chemical Corp., Richmond, Va.) was added to the same gasoline asin Run 1 in the same set of injectors, but cleaned between tests. Thefriction modifier was a low molecular weight amide made from a (C18)branched fatty acid reacted with diethanolamine. Injector 1 2 3 4 4.06.0 5.4 5.0 = 5.1% average

Run 3: Base fuel gasoline with no fuel additive composition. Injector 12 3 4 31.0 33.5 25.1 6.6 = 24.1% average

Example 2

The fuel additive composition identified in Example 1 was used in a basefuel with and without the addition of a friction modifier, such as thedisclosed amide. The fuel was tested in a model year 2000 to 2002 GMAstro Van with a 4.3-L V-6 engine, which was equipped with sequentialcentral port fuel injection (SCPI). The fuel injector fouling initialperformance standard as detailed in the “TOP TIER Detergent GasolineDeposit Control Performance Standards,” released in April 2004, wasused. A pass occurs when the vehicle “sticks” no more than one injector.

The data is as follows: Fuel Additive of Friction No. Stuck Test No.Example 1 modifier Injector Vehicle Result 1 (not 80 ptb 0 ptb 2 Failinventive) 2 (not 80 ptb 0 ptb 2 Fail inventive) 3 (inventive) 80 ptb 20ptb  0 Pass

HiTEC® 6457, which is a reaction product of isostearic acid anddiethanolamine, was used as the friction modifier.

As can be seen from the data, a vehicle which uses a fuel compositioncomprising a fuel additive composition without a friction modifierresulted in a higher percentage of deposits (see Run 1 of Example 1) andmore stuck injectors (see Test Nos. 1 and 2 of Example 2) as compared toa fuel composition comprising a fuel additive composition with afriction modifier.

Example 3

A mileage accumulation test was done on a Chassis Dynamometer, with amixed highway and city driving cycle. In particular, the driving cyclewas 76 miles, for 99:46 minutes, at an average speed of 45.7 mph. Tworuns with different formulations were tested. The first one did notcomprise a friction modifier. The second run did comprise a frictionmodifier. For the test, a 2000 Mercury Marquis 4.6-L V8 engine was used.The average intake deposits were measured after a 1500 mile dirty up ona PUL fuel. Moreover, the average chamber head and piston-top depositswere measured after a 5000 mile clean up on the fuel additive in the PULfuel at treat rates as indicated in the table (ptb). Clean-Up PhaseDirty-Up Avg Avg Phase Chamber Piston- Total Avg Intake Avg Intake % IVDHead Top Chamber Total Deposit Deposit Clean Up Deposit Deposit DepositDeposits Run 1 (not 615.9 176.6 71.3% 901.3 1103.5 2004.8 2181.4inventive) Run 2 856.4 250.6 70.7% 817.9 932.5 1750.4 2001.0 (inventive)Component Run 1 Run 2 HiTEC 6416 55 55 Polyetheramine 20 20 Actaclear 2222 HiTEC 6457  0 60

As can be seen, the second run with the formulation comprising afriction modifier exhibited less average chamber head and piston-topdeposits, and therefore less total chamber deposits.

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the disclosure are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Moreover, all ranges disclosed hereinare to be understood to encompass any and all subranges subsumedtherein. For example, a range of “less than 10” includes any and allsubranges between (and including) the minimum value of zero and themaximum value of 10, that is, any and all subranges having a minimumvalue of equal to or greater than zero and a maximum value of equal toor less than 10, e.g., 1 to 5.

It is noted that, as used in this specification and the appended claims,the singular forms “a,” “an,” and “the,” include plural referents unlessexpressly and unequivocally limited to one referent. Thus, for example,reference to “a friction modifier” includes two or more differentfriction modifiers. As used herein, the term “include” and itsgrammatical variants are intended to be non-limiting, such thatrecitation of items in a list is not to the exclusion of other likeitems that can be substituted or added to the listed items.

It will be apparent to those skilled in the art that variousmodifications and variations can be made to various embodimentsdescribed herein without departing from the spirit or scope of thepresent teachings. Thus, it is intended that the various embodimentsdescribed herein cover other modifications and variations within thescope of the appended claims and their equivalents.

1. A fuel additive composition comprising: a) a Mannich product, b) apolyetheramine, and c) a friction modifier.
 2. The composition of claim1, wherein the Mannich product is a reaction product of analkyl-substituted hydroxyaromatic compound, an aldehyde, and an amine.3. The composition of claim 2, wherein the alkyl-substitutedhydroxyaromatic compound is chosen from alkylphenols.
 4. The compositionaccording to claim 3, wherein the alkylphenols are chosen from cresols.5. The composition according to claim 2, wherein the alkyl-substitutedhydroxyaromatic compound is chosen from polyolefin-substituted phenols.6. The composition according to claim 5, wherein thepolyolefin-substituted phenols are chosen from polybutylene-substitutedphenols and polypropylene-substituted phenols.
 7. The compositionaccording to claim 5, wherein the polyolefin-substituted phenols arepolyisobutylcresols.
 8. The composition according to claim 2, whereinthe amine comprises an alkylene polyamine.
 9. The composition accordingto claim 1, further comprising a polyether alcohol.
 10. The compositionaccording to claim 2, wherein the aldehyde is formaldehyde or aprecursor thereof.
 11. The composition according to claim 1, wherein thefriction modifier is an amide.
 12. The composition according to claim11, wherein the amide is an alkanolamide.
 13. The composition accordingto claim 11, wherein the amide is a reaction product of an acid and anamine.
 14. The composition according to claim 13, wherein the acid isselected from the group consisting of a monofunctional acid and amultifunctional acid.
 15. The composition according to claim 13, whereinthe amine is selected from the group consisting of a monoamine and apolyamine.
 16. The composition according to claim 13, wherein the acidis a monocarboxylic fatty acid and the amine is diethanolamine.
 17. Thecomposition according to claim 1, wherein the Mannich product iscombined with at least one liquid carrier.
 18. A process for preparing afuel additive, comprising providing a Mannich product, a polyetheramine,and a friction modifier to yield a fuel additive.
 19. The processaccording to claim 18, wherein the friction modifier is present in thefuel additive in a friction modifying amount via ASTM D
 6079. 20. A fuelcomposition comprising: (A) a fuel in a major amount; and (B) a fueladditive composition according to claim 1 in a minor amount.
 21. Thecomposition according to claim 20, wherein the fuel comprises gasoline.22. The composition according to claim 20, wherein the Mannich productcomprises from about 5 ptb to about 300 ptb of active material in thefuel composition.
 23. The composition according to claim 22, wherein theMannich product comprises from about 25 ptb to about 200 ptb of activematerial in the fuel composition.
 24. The composition according to claim20, wherein the polyetheramine comprises from about 5 ptb to about 300ptb of active material in the fuel composition.
 25. The compositionaccording to claim 24, wherein the polyetheramine comprises from about25 to about 200 ptb of active material in the fuel composition.
 26. Thecomposition according to claim 20, further comprising at least oneadditive selected from the group consisting of dispersants, detergents,antioxidants, carrier fluids, metal deactivators, dyes, markers,corrosion inhibitors, biocides, antistatic additives, drag-reducingagents, demulsifiers, dehazers, anti-icing additives, anti-knockadditives, anti-valve-seat recession additives, lubricity additives, andcombustion improvers.
 27. A method for preventing and/or reducing theformation of deposits in an engine, comprising fueling and operatingsaid engine with a fuel composition according to claim
 20. 28. Themethod of claim 27, wherein the deposits are combustion chamberdeposits.
 29. An engine combusting a fuel additive composition accordingto claim
 1. 30. An engine combusting a fuel composition according toclaim
 20. 31. An actuated injector contacting a fuel additivecomposition according to claim
 1. 32. An actuated injector contacting afuel composition according to claim
 20. 33. The injector of claim 31,wherein the actuated injector is selected from the group consisting ofdirect-injection gasoline, port-fuel, sequential central port-fuel, anddirector plate injectors.
 34. A fuel additive composition comprising: a)an aliphatic hydrocarbyl-substituted amine, b) a polyetheramine, and c)a friction modifier.